TW202012680A - Substrate, selective method for accumulating film on metal surface region of substrate, accumulated film of organic matter, and organic matter - Google Patents

Abstract

This selective method for accumulating a film on a metal surface region of a substrate is characterized in that a film of organic matter represented by general formula (1) is selectively accumulated on a substrate having a structure in which both of a first surface region that includes metal and a second surface region that includes a non-metal inorganic material and/or a metal oxide are exposed, the film being accumulated to a greater extent in the first surface region than in the second surface region. (In general formula (1), N represents a nitrogen atom, and X represents an oxygen atom or a sulfur atom. R1 represents a C2-12 hydrocarbon group that may have a hetero atom or a halogen atom, and R2, R3, and R4 each independently represent a hydrogen atom or a C1-10 hydrocarbon group that may have a hetero atom or a halogen atom. In the case of a C3 or higher hydrocarbon group, a branched or cyclic hydrocarbon group is also included.).

Description

Substrate, selective film stacking method on metal surface area of substrate, stacked film of organic matter and organic matter

The invention is a substrate, a selective film deposition method for a metal surface area of a substrate, a deposition film of organic matter and organic matter.

In recent years, the structure of semiconductor wafers has become increasingly miniaturized, and the previous lithography method that patterned by selectively removing a part of the structure has problems such as a large number of steps or high cost. It is considered that if the chemical vapor deposition (CVD) method or the atomic layer deposition (ALD) method can selectively form a film on a desired portion on the substrate, it becomes the optimal process for forming a fine structure to solve these problems.

However, for a substrate having a plurality of surface areas of different materials such as metals used for electrodes or wiring, or inorganic dielectrics used for insulating films, when a film is selectively deposited by CVD or ALD, The barrier films must be selectively stacked, but the previous methods are not sufficiently selective.

Regarding the formation method of the selective film, a method of depositing materials that hinder the accumulation of the film in a region where the film is not to be formed is known. For example, Patent Document 1 discloses a method for forming a thin film pattern of an inorganic material such as TiN, AlN, or SiN on a substrate by atomic layer deposition (ALD), and includes the following steps: using fluorine on the substrate Atomic layer deposition hindering material for fluorine-containing resins with a content of 30 atomic% or more, having at least one tertiary or quaternary carbon, and having no ester group, hydroxyl group, carboxyl group, or imide group, by screen printing, etc. The pattern of the atomic layer deposition barrier layer is formed. Secondly, by the atomic layer deposition method, a layer of inorganic material is formed in the area where the atomic layer deposition barrier layer does not exist.

In addition, Patent Document 2 discloses a method for selectively depositing layers on a substrate having an exposed metal surface and an exposed silicon-containing surface, and includes the following steps: (a) on the exposed metal surface Depositing a first self-assembled monomolecular film on top; (b) depositing a second self-assembled monomolecular film as an organic silane system on the exposed silicon-containing surface; (c) heating the above substrate and heating the first The assembled monomolecular film is removed from the exposed metal surface; (d) a layer as a low dielectric constant or metal layer is selectively deposited on the exposed metal surface; and (e) the substrate is heated , The second self-assembled monomolecular film is removed from the exposed silicon-containing surface.

According to the above method, for a substrate having a first surface and a second surface including different materials, the difference in the surface states of the two can be used to preferentially deposit a film on the first surface compared to the second surface. In addition, according to the above method, the number of steps in the process of forming a fine structure can be reduced.

For example, Patent Document 3 discloses a process of performing a step including contacting a first gas-phase precursor substance and a second step on a substrate including a first surface as a metallic surface and a second surface as a dielectric surface The accumulation cycle of the step of contacting the gas-phase precursor substance is more likely to selectively form an organic thin film on the first surface than on the second surface. In Example 1 of Patent Document 3, the following content is described: a 200 mm silicon wafer with tungsten (W) characteristics alternating with the surface of silicon oxide is used as a substrate, using 1,6-diaminohexane (DAH) and Pyromellitic dianhydride (PMDA) is subjected to 250-1000 stacking cycles to form a polyimide film. The thickness of the polyimide film on the surface of metal tungsten is thicker than the thickness of the polyimide film on the surface of SiO ₂ .

Patent Document 4 discloses a method of selectively forming a passivation layer on a first surface made of metal using the selective deposition method of an organic film described in Patent Document 3, and then forming only a second surface on a dielectric body Layer X; and then use this method to form the metallization structure of the integrated circuit.

Patent Document 5 discloses a method of forming a monomolecular film on a metal surface by coordination bonds. [Prior Technical Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2016/147941 [Patent Document 2] Japanese Patent Special Publication No. 2018-512504 [Patent Document 3] Japanese Patent Laid-Open No. 2017-216448 [Patent Document 4] Japanese Patent Laid-Open No. 2018-137435 [Patent Document 5] Japanese Patent Laid-Open No. 10-180929

[Problems to be solved by the invention]

However, Patent Document 1 does not disclose the following method: using an atomic layer deposition barrier material on a single material substrate to form a specific pattern, and for a substrate having a plurality of surface areas with different materials, selectivity in a desired surface area To form a structure.

In Patent Document 2, the step of forming the first SAM (Self-Assembled Monolayer) film on the metal surface is to immerse the substrate in a long-chain alkyl mercaptan, long-chain organic phosphonic acid, long-chain sulfonic acid The method in the solution is the so-called wet process. On the other hand, the ALD or CVD process used for the low dielectric constant dielectric layer or metal layer on the substrate after the formation of the SAM film is a dry process, so the dry process must be performed after the wet process, the method changes It is complicated, and a method of forming a barrier film is expected in the dry process.

Although the methods for selectively forming organic thin films described in Patent Document 3 and Patent Document 4 are dry processes, it is necessary to repeatedly switch the stacking cycle of the raw material and the temperature, and it takes a lot of time to form the organic thin film.

Although Patent Document 5 discloses a method of forming a monomolecular film, it does not mention the formation of a selective film.

The object of the present invention is to provide a method, a substrate obtained by the above method, a deposited film of organic matter, and an organic matter in view of the above problems; the above method is a simple operation, compared to the exposed surface of the non-metallic inorganic material on the substrate Areas or exposed surface areas of metal oxides are more likely to selectively deposit organic films on exposed surface areas of metals. [Technical means to solve the problem]

The present inventors conducted intensive research and found that the organic substance represented by the following general formula (1) is more inclined than the surface area where the non-metallic inorganic material on the substrate is exposed or the surface area where the metal oxide is exposed The present invention has been completed by selectively depositing a film of organic matter on the exposed surface area of the metal.

(於通式(1)中，N為氮原子，X為氧原子或硫原子； R¹ 為可具有碳數2～12之雜原子或鹵素原子之烴基，R² 、R³ 、R⁴ 分別獨立為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)The selective film deposition method of the metal surface region of the substrate of the present invention is characterized in that both the first surface region including metal and the second surface region including non-metallic inorganic material and/or metal oxide are exposed Compared with the second surface area, the structured substrate is more likely to selectively deposit a film of an organic substance represented by the following general formula (1) on the first surface area. [Chemical 1]

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ and R ⁴ are respectively (A hydrocarbon group independently a hydrogen atom or a hydrocarbon group which may have a ring or heteroatom or a halogen atom with a carbon number of 1 to 10; wherein, the hydrocarbon also includes a branched or cyclic structure when the carbon number is 3 or more)

According to the above method, the following method can be provided: By using the organic substance represented by the general formula (1), compared with the second surface area on the substrate including the exposed area of the non-metallic inorganic material and/or the exposed area of the metal oxide It is more likely to selectively deposit organic films on the first surface area containing the exposed areas of the metal.

In the above-mentioned second surface area, non-metal inorganic materials can be exposed, metal oxides can be exposed, both non-metal inorganic materials and metal oxides can be exposed, except for metals, non-metal inorganic materials and metal oxides The substance is exposed. That is, the second surface region includes a region where at least one of the non-metallic inorganic material and the metal oxide is exposed. The second surface area may be an area where only at least one of the non-metallic inorganic material and the metal oxide is exposed. The first surface area may be an area where only metal is exposed.

(於通式(1)中，N為氮原子，X為氧原子或硫原子； R¹ 為可具有碳數2～12之雜原子或鹵素原子之烴基，R² 、R³ 、R⁴ 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，上述烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)The substrate of the present invention is characterized in that it has a structure in which both a first surface area including metal and a second surface area including non-metallic inorganic material and/or metal oxide are exposed, and is on the first surface area The film having the organic substance represented by the following general formula (1) does not have the film of the organic substance in the second surface area, or the thickness t ₂ of the film of the organic substance on the second surface area is thinner than the first surface The thickness t ₁ of the film of the above organic substance on the area. [Chem 2]

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ , and R ⁴ are (A hydrogen atom or a hydrocarbon group which may have a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; where the above hydrocarbons also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more)

According to the above substrate, the following substrate can be provided: by using the organic substance represented by the general formula (1), compared to the second surface area on the substrate including the exposed area of the non-metallic inorganic material and/or the exposed area of the metal oxide It is more likely to selectively deposit organic films on the first surface area containing the exposed areas of the metal.

(於通式(1)中，N為氮原子，X為氧原子或硫原子； R¹ 為可具有碳數2～12之雜原子或鹵素原子之烴基，R² 、R³ 、R⁴ 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)The deposited film of an organic substance of the present invention is characterized in that it is a film of an organic substance formed by the above method and is selectively deposited on a substrate. The organic substance is represented by the following general formula (1). [Chemical 3]

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ , and R ⁴ are (A hydrogen atom or a hydrocarbon group which may have a ring of 1 to 10 carbon atoms or a heteroatom or a halogen atom; wherein the hydrocarbon group may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more)

(於通式(1)中，N為氮原子，X為氧原子或硫原子； R¹ 為可具有碳數2～12之雜原子或鹵素原子之烴基，R² 、R³ 、R⁴ 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)The organic substance of the present invention is characterized by a selective film deposition method for the metal surface area of the substrate, and is represented by the following general formula (1). [Chemical 4]

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ , and R ⁴ are (A hydrogen atom or a hydrocarbon group which may have a ring of 1 to 10 carbon atoms or a heteroatom or a halogen atom; wherein the hydrocarbon group may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more)

By using the organic substance of the present invention, the first surface region including the exposed metal region can be more preferred than the second surface region including the exposed region of the non-metallic inorganic material and/or the exposed region of the metal oxide on the substrate The surface area selectively accumulates organic films.

(於通式(1)中，N為氮原子，X為氧原子或硫原子； R¹ 為可具有碳數2～12之雜原子或鹵素原子之烴基，R² 、R³ 、R⁴ 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基) [發明之效果]The solution of the present invention is characterized by containing an organic substance and a solvent characterized by the following general formula (1). [Chem 5]

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ , and R ⁴ are Hydrogen atom or a hydrocarbon group which may have a ring having 1 to 10 carbon atoms or a hetero atom or a halogen atom; wherein the hydrocarbon may also include a hydrocarbon group having a branched or cyclic structure when the carbon number is 3 or more) [Effect of the invention]

According to the method of the present invention, by using the organic substance represented by the general formula (1), the following method can be provided: Compared with the second on the substrate including the exposed area of the non-metallic inorganic material and/or the exposed area of the metal oxide The surface area is more likely to selectively deposit a film of organic matter on the first surface area including the exposed area of the metal.

Furthermore, according to the substrate of the present invention, by using the organic substance represented by the general formula (1), it is possible to provide the following substrate: compared to the area on the substrate including the exposed area of the non-metallic inorganic material and/or the exposed area of the metal oxide The second surface area is more likely to selectively deposit a film of organic matter on the first surface area including the exposed area of the metal.

Hereinafter, the present invention will be described in detail, but the description of the constituent elements described below is an example of an embodiment of the present invention and is not limited to these specific contents. It can be implemented after making various changes within the scope of its thrust.

The selective film deposition method for the metal surface area of the substrate according to the embodiment of the present invention is characterized by both the first surface area including metal and the second surface area including non-metallic inorganic material and/or metal oxide Compared to the second surface area, the substrates of all exposed structures are more likely to selectively deposit organic films represented by the general formula (1) on the first surface area.

In the above method, the film of the organic substance represented by the general formula (1) is more selectively deposited than the second surface area. At this time, it is preferable to deposit on the substrate in such a manner that the film of the organic substance is selectively deposited only on the first surface area, and the film of the organic substance is not deposited on the second surface area, or on the first surface area The thickness t ₁ of the organic film is thicker than the thickness t ₂ of the organic film on the second surface area, and the value of t ₁ /t ₂ obtained by dividing t ₁ by t ₂ is 5 or more. The value of t ₁ /t ₂ is preferably 10 or more, and more preferably 100 or more. Furthermore, t _{1 is} preferably 1 nm or more, more preferably 2 nm or more, preferably 200 nm or less, and more preferably 100 nm or less. In addition, t _{2 is} preferably less than 1 nm, and may be 0 nm. The thickness of t ₁ and t ₂ can be measured by an atomic force microscope (AFM). The case where t ₂ is 0 nm means the above condition, that is, the film of the organic substance is selectively deposited only on the first surface area.

As the metal constituting the first surface region, Cu, Co, Ru, Ni, Pt, Al, Ta, Ti, and Hf can be used, and Cu, Co, and Ru are particularly preferably used. Furthermore, the metal constituting the first surface area may also be an alloy of the aforementioned metals.

Examples of the metal oxide constituting the second surface region include oxides of the above metals.

Examples of the non-metal inorganic material constituting the second surface area include silicon-based materials such as silicon, silicon oxide, silicon nitride, and silicon oxynitride, and germanium, germanium oxide, germanium nitride, and germanium oxynitride. Among the non-metal inorganic materials, the germanium-based materials are preferably silicon-based materials. The above silicon includes both polycrystalline silicon and single crystal silicon. Silicon oxide is represented by the chemical formula of SiO _x (x is 1 or more and 2 or less), and is usually SiO ₂ . The silicon nitride is represented by the chemical formula of SiN _x (x is 0.3 or more and 9 or less), and is usually Si ₃ N ₄ . The silicon oxynitride is represented by Si ₄ O _x N _y (x is 3 or more and 6 or less, and y is 2 or more and 4 or less), for example, Si ₄ O ₅ N ₃ .

As a method of obtaining the first surface region containing metal, a method of obtaining a film of metal using a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD) method, or the like can be mentioned. For example, by forming a metal film on the non-metal inorganic material or metal oxide film by the above method, forming the metal film into a specific pattern by photolithography, or using a non-metal inorganic material or metal A hole or groove is formed in the oxide film, and a method of embedding metal in the groove can obtain a structure in which both the first surface area including metal and the second surface area including non-metallic inorganic material and/or metal oxide are exposed Of the substrate.

For example, as the substrate used in the method of the present invention, it is a substrate of a semiconductor device having a metal film in its structure or a substrate in which a metal film is formed in the patterning step of the semiconductor device, etc. In particular, it can be exemplified in the formation of an insulating film of a semiconductor element A substrate made of metal wiring with a specific pattern. That is, as the first surface area, the metal wiring conforms, and as the second surface area, the insulating film including the non-metallic inorganic material and/or the metal oxide conforms. However, the substrate used in the selective film deposition method of the metal surface area of the substrate of the present invention is not limited to these members.

(於通式(1)中，N為氮原子，X為氧原子或硫原子； R¹ 為可具有碳數2～12之雜原子或鹵素原子之烴基，R² 、R³ 、R⁴ 分別獨立為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)As the organic substance, an organic substance represented by the following general formula (1) is used. [化6]

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ and R ⁴ are respectively (A hydrocarbon group independently a hydrogen atom or a hydrocarbon group which may have a ring or heteroatom or a halogen atom with a carbon number of 1 to 10; wherein, when the carbon number is 3 or more, the hydrocarbon group may also include a branched or cyclic structure)

Examples of the hetero atom of R ¹ to R ⁴ include nitrogen atom, oxygen atom, sulfur atom, and phosphorus atom. Examples of R ¹ include C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , C ₅ H ₁₀ , C ₆ H ₁₂ , and phenyl. A part of the phenyl group may be hydrocarbyl, hydroxyl, thiol, Substitution with amine groups, halogens, etc. Examples of R ² , R ³ , and R ⁴ include hydrogen groups and hydrocarbon groups such as CH ₃ , C ₂ H ₅ , and C ₃ H ₇ . A part of the hydrocarbon group constituting R ² , R ³ , and R ⁴ may be substituted with a hydroxyl group, a thiol group, an amine group, a halogen, or the like. Furthermore, when both R ³ and R ⁴ have a carbon number of 1 or more, R ³ and R ⁴ may be directly bonded, and the general formula (1) may adopt a ring structure. R ² , R ³ , and R ⁴ may be the same substituent, or may be different substituents.

Particularly preferred is an organic substance represented by the general formula (1), preferably a compound in which R ² and R ³ are hydrogen atoms and have an amine group (-NH ₂ ). Further preferably, R ⁴ is a hydrogen atom, and -XR ⁴ is a compound as a hydroxyl group (-OH) or a thiol group (-SH).

Specific compounds represented by the general formula (1) include, for example, o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2-(ethylamino)ethanol, 2-amine Ethyl mercaptan, 3-amino-1-propanol, o-aminophenol, etc. Among these, o-aminothiophenol or 2-aminobenzyl alcohol is preferred. These compounds can be used alone or in combination.

As a specific method that prefers to selectively deposit a film of organic matter represented by the general formula (1) on the first surface area compared to the second surface area, the substrate may be exposed to a solution containing organic matter and a solvent The method (wet method) and the method of exposing the above substrate to an atmosphere containing organic matter (dry method) are two methods. Hereinafter, these methods will be described.

[Wet method] In the wet method of the embodiment of the present invention, the substrate is exposed to a solution containing the above-mentioned organic substance and solvent. As an example, by immersing the substrate having the first surface area and the second surface area in the solution containing organic substance and solvent In the solution, a film deposition step of contacting the surface of the substrate with the solution and selectively depositing a film of organic matter on the first surface area of the substrate may be performed. As a method of exposing the substrate to the solution, in addition to the dipping method, a spin coating method for dropping the solution onto the substrate and rotating it at a high speed or a spray method for spraying the solution on the substrate can also be used.

The concentration of the organic substance in the above solution is preferably 0.1% by mass or more and 10% by mass or less relative to the total of the organic substance and the solvent, more preferably 0.5% by mass or more and 8% by mass or less, and particularly preferably 1% by mass or more and 5% by mass or less .

The solvent used in the solution is not particularly limited, but it is preferable to use an organic solvent capable of dissolving organic substances, and examples thereof include alcohols such as ethanol and isopropyl alcohol (IPA).

The temperature of the solution in the wet film deposition step is preferably 0 to 80°C, and the time for immersing the substrate in the solution is preferably 1 to 1000 seconds. When the substrate is immersed in the above solution, the solution is preferably stirred by a stirring blade or the like.

In addition, after immersing the substrate in a solution containing an organic substance, it is preferable to perform a washing step of pulling the substrate and washing the substrate with a solvent. Examples of the solvent that can be used in the washing step include the above-mentioned organic solvents. As a washing method, it is preferable to immerse in the above solvent at 0 to 80°C for 1 to 1000 seconds.

After the above washing step, it is preferable to dry the substrate by blowing an inert gas such as nitrogen or argon on the substrate. The temperature of the inert gas to be blown is preferably 0 to 80°C.

[Dry method] In the dry method according to the embodiment of the present invention, the above substrate is exposed to an atmosphere containing an organic substance, specifically, by placing the substrate in a chamber and introducing the organic substance-containing gas into the chamber, The step of depositing the organic-containing gas in contact with the surface of the substrate to selectively deposit the organic film on the first surface area of the substrate.

As the organic substance used in the dry film deposition step, the organic substance represented by the general formula (1) is preferably the same as the wet method.

The temperature of the atmosphere gas in the chamber containing the organic substance gas is preferably 0°C or more and 200°C or less, more preferably 40°C or more and 200°C or less, and particularly preferably 60°C or more and 180°C or less.

The pressure range of the atmosphere gas in the chamber containing the organic substance gas is preferably 0.1 Torr (13 Pa) or more and 500 Torr (67 kPa) or less, more preferably 1 Torr (0.13 kPa) or more and 100 Torr (13 kPa) or less.

Furthermore, in order for organic matter to contact the substrate in the form of gas, the temperature and pressure in the chamber must be set to the condition where the organic matter is in a gaseous state.

In the atmosphere gas in the chamber, it is preferably a gas containing 1% by volume or more and 100% by volume or less of organic matter, more preferably 10% by volume or more and 100% by volume or less, and still more preferably 50% by volume or more and 100% by volume the following.

Gaseous organic matter can be obtained by depressurizing and/or heating liquid organic matter, and gaseous organic matter diluted by inert gas can also be obtained by passing inert gas to the liquid organic matter. As the inert gas, nitrogen, argon, krypton, neon, etc. can be used.

After performing the dry film deposition step, the excess organic matter can be removed by depressurizing the chamber to 1-100 Pa. In the dry method, no drying step is required.

By using the above-mentioned wet method or the above-mentioned dry method of the present invention, the surface area exposed by the non-metallic inorganic material or the surface area exposed by the metal oxide on the substrate is more likely to be The exposed surface area selectively deposits organic films.

By performing the above-mentioned wet method or the above-mentioned dry method, the deposited film of the organic substance represented by the general formula (1) selectively deposited on the substrate also corresponds to one embodiment of the deposited film of the organic substance of the present invention.

(於通式(1)中，N為氮原子，X為氧原子或硫原子； R¹ 為可具有碳數2～12之雜原子或鹵素原子之烴基，R² 、R³ 、R⁴ 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，上述烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)[Substrate after selective stacking] The substrate of the present invention is characterized in that it has a structure in which both the first surface area containing metal and the second surface area containing non-metallic inorganic material and/or metal oxide are exposed And the film of the organic substance represented by the following general formula (1) in the first surface area, the film of the organic substance not in the second surface area, or the film of the organic substance on the second surface area The thickness t _{2 is} thinner than the thickness t ₁ of the film of the organic substance on the first surface area. [化7]

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ , and R ⁴ are (A hydrogen atom or a hydrocarbon group which may have a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; where the above hydrocarbons also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more)

In the substrate of the present invention, as described above, the film of the organic substance represented by the following general formula (1) is provided in the first surface area, and the film of the organic substance is not provided in the second surface area, or the second surface The thickness t ₂ of the organic film on the area is thinner than the thickness t ₁ of the organic film on the first surface area.

In the substrate of the present invention, when the thickness t ₂ of the organic film on the second surface area is thinner than the thickness t ₁ of the organic film on the first surface area, it is more preferably obtained by dividing t ₁ by t ₂ The value of t ₁ /t ₂ is 5 or more. The value of t ₁ /t ₂ is preferably 10 or more, and more preferably 100 or more. Furthermore, t _{1 is} preferably 1 nm or more, more preferably 2 nm or more, preferably 200 nm or less, and more preferably 100 nm or less. In addition, t _{2 is} preferably less than 1 nm, and may be 0 nm. The thickness of t ₁ and t ₂ can be measured by an atomic force microscope (AFM). When t ₂ is 0 nm, it is the above-mentioned condition, that is, the film of the organic substance is selectively deposited only on the first surface area.

In the substrate of the present invention, regarding the first surface area containing metal, the second surface area containing non-metallic inorganic material and/or metal oxide, the organic matter represented by the general formula (1), etc. The selective film deposition method of the metal surface area of the substrate is described, so detailed description is omitted here.

It is considered that the film of the above-mentioned organic substance is formed by interaction between a group having a nitrogen atom, an oxygen atom or a sulfur atom in the molecule of the above-mentioned organic substance and the metal in the first surface region. [Example]

Hereinafter, it was confirmed by the following experiment that a film can be selectively deposited by an organic substance on the surface area where the metal is exposed.

[Experiment Example 1-1] Dissolve 1% of o-aminothiophenol in isopropanol (hereinafter referred to as IPA) to prepare a solution containing o-aminothiothiol as an organic substance and a solvent. Next, the substrate containing the Cu surface was immersed in this solution for 60 seconds to deposit the organic film. The temperature of the solution is 20-25°C. After that, it was immersed in an IPA solution at 20 to 25°C for 60 seconds and performed twice to remove excess organic matter, followed by blowing nitrogen at 20 to 25°C for 60 seconds to dry the substrate. The thickness of the organic substance formed on the substrate was measured by an atomic force microscope (AFM). The result was 48 nm. Furthermore, the elemental composition was analyzed by X-ray photoelectron spectroscopy (XPS), and as a result, strong spikes of nitrogen and sulfur were confirmed.

[Experiment example 1-2～1-24] Except that the type of metal, organic substance, type of solvent, solution concentration, etc. on the surface of the substrate were changed as shown in Table 1, the evaluation was carried out in the same manner as in Experimental Example 1-1. The results are shown in Table 1.

[Experimental Example 2-1] Dissolve 5% o-aminothiophenol in IPA to prepare a solution containing o-aminothiothiol as an organic substance and a solvent. Next, the substrate containing the Si surface was immersed in this solution for 60 seconds to deposit a film of organic matter. The temperature of the solution is 20-25°C. After that, it was immersed in an IPA liquid at 20 to 25°C for 60 seconds and performed twice to remove excess organic matter, and nitrogen gas at 20 to 25°C was blown for 60 seconds to dry the substrate. The film thickness of the organic substance formed on the substrate was measured by AFM, and the result was 0 nm. Furthermore, the elemental composition was analyzed by XPS, and as a result, peaks of nitrogen and sulfur could not be confirmed.

[Experiment Example 2-2～2-10] Except that the type of metal, organic substance, type of solvent, solution concentration, etc. on the surface of the substrate were changed as shown in Table 2, the evaluation was carried out in the same manner as in Experimental Example 2-1. The results are shown in Table 2.

[Experiment Example 3-1] A substrate containing a Cu surface was installed in a chamber capable of vacuum processing, and the chamber pressure was set to 1 Torr (0.13 kPa, absolute pressure). Next, the cylinder of o-aminothiophenol that was connected to the chamber was heated to 80°C, the valve was opened, and the gas of o-aminothiophenol was fed into the chamber to deposit organic films on the substrate containing Cu. Furthermore, the temperature of the chamber is set to be the same as the temperature of the cylinder, and the temperature of the gas of o-aminothiophenol is kept to be the same as the temperature of keeping the cylinder warm until it contacts the substrate. After the organic matter is deposited on the film, the chamber is decompressed to 0.1 Torr (13 Pa) to remove excess organic matter. The film thickness of the organic substance formed on the substrate was measured by AFM, and the result was 10 nm. Furthermore, the elemental composition was analyzed by XPS, and as a result, strong spikes of nitrogen and sulfur were confirmed.

[Experiment Example 3-2～3-12] Except that the types of metals and organic substances on the substrate, the temperature of the cylinder holding temperature (organic substance heating temperature), the chamber pressure, and the like were changed as shown in Table 3, the evaluation was carried out in the same manner as in Experimental Example 3-1. The results are shown in Table 3.

[Experiment Example 4-1] A substrate containing a Si surface was placed in a chamber capable of vacuum processing, and the chamber pressure was set to 10 Torr. Next, the cylinder of o-aminothiophenol connected to the chamber is heated to 120°C, the valve is opened, the gas of o-aminothiophenol is supplied into the chamber, and the organic film is deposited on the substrate containing the Si surface . After the organic matter is deposited on the film, the chamber is decompressed to 0.1 Torr to remove excess organic matter. The film thickness of the organic substance formed on the substrate was measured by AFM, and the result was 0 nm. Furthermore, the elemental composition was analyzed by XPS, and as a result, peaks of nitrogen and sulfur could not be confirmed.

[Experiment Example 4-2～4-10] Except for changing the types of metals and organic substances on the substrate, the temperature for holding the cylinder, the chamber pressure, etc., as shown in Table 4, the evaluation was carried out in the same manner as in Experimental Example 4-1. The results are shown in Table 4.

In addition, in the above-mentioned experimental example, the substrate containing the Cu surface was prepared by depositing a copper film with a thickness of about 100 nm on a silicon substrate by vapor deposition, and then removing the natural oxide film on the surface. The substrate containing the Co surface is produced by: depositing a cobalt film with a thickness of about 100 nm on a silicon substrate by evaporation, and then removing the natural oxide film on the surface. The substrate containing the Ru surface is produced by the following method: after depositing a ruthenium film with a thickness of about 100 nm on a silicon substrate by evaporation, the natural oxide film on the surface is removed.

In addition, the substrate containing the Si surface is produced by removing the natural oxide film of the silicon substrate. The substrate containing the SiO ₂ surface is produced by forming a silicon dioxide film on the silicon substrate with a thickness of about 30 nm by chemical vapor deposition. The substrate containing the SiN surface is produced by forming a silicon nitride film represented by the chemical formula of Si ₃ N ₄ on the silicon substrate with a thickness of about 30 nm using a chemical vapor deposition method. The substrate containing the SiON surface is produced by: forming a SiN surface on a silicon substrate by chemical vapor deposition and then oxidizing it to form a film of Si ₄ O _x N _y (x is 3 or more) with a thickness of about 10 nm 6 or less, y is 2 or more and 4 or less) the silicon oxynitride film represented by the chemical formula. A substrate containing a CuO surface is produced by depositing a copper oxide film with a thickness of about 100 nm on a silicon substrate by evaporation. The substrate containing the CoO surface is produced by depositing a cobalt oxide film with a thickness of about 100 nm on a silicon substrate by evaporation.

The above results are summarized in Tables 1 to 4 below.

[Table 1]

[Table 2]

[table 3]

[Table 4]

From the results shown in Tables 1 to 4, it can be seen that in the above experimental examples, organic materials deposited films on metals such as Cu, Co, Ru, but on non-metallic inorganic materials such as Si, SiO ₂ , SiN, SiON, or CuO, No film is deposited on metal oxides such as CoO. Therefore, in the case of using a substrate having a surface area exposed by a metal and a surface area exposed by a non-metallic inorganic material or a surface area exposed by a metal oxide, by using the organic substances shown in Tables 1 to 4, it is possible to use only organic materials The exposed surface area selectively deposits a film.

In addition, the organic substance represented by the general formula (1) is not only Co, Cu, Ru, but also metals such as Ni, Pt, Al, Ta, Ti, Hf, etc., which are wiring materials for semiconductor devices, etc. or conductive materials suitable for electrode materials. The film can also be deposited on top.

Claims (18)

A method characterized in that, for a substrate having a structure in which both a first surface area containing a metal and a second surface area containing a non-metallic inorganic material and/or a metal oxide are exposed, compared to the second surface area, It is more likely to selectively deposit organic films represented by the following general formula (1) on the first surface area;

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom having 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ and R ⁴ are respectively A hydrocarbon group independently a hydrogen atom or a hydrocarbon group that may have a ring or heteroatom or a halogen atom with a carbon number of 1 to 10; where the hydrocarbon is based on a carbon number of 3 or more, it also includes a branched or cyclic hydrocarbon group). The method of claim 1, wherein the metal is at least one selected from the group consisting of Cu, Co, Ru, Ni, Pt, Al, Ta, Ti, and Hf. The method according to claim 1 or 2, wherein the non-metallic inorganic material is at least one selected from the group consisting of silicon, silicon oxide, silicon nitride, and silicon oxynitride. The method according to any one of claims 1 to 3, wherein the metal oxide is an oxide of at least one metal selected from the group consisting of Cu, Co, Ru, Ni, Pt, Al, Ta, Ti, and Hf . The method according to any one of claims 1 to 4, wherein in the above general formula (1), R ² , R ³ and R ⁴ are hydrogen atoms. The method according to claim 1, wherein the organic substance is selected from the group consisting of o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2-(ethylamino)ethanol, 2-aminoethylthiol At least one of the group consisting of 3-amino-1-propanol and o-aminophenol. The method according to any one of claims 1 to 6, wherein the step of preferentially depositing a film of organic matter on the first surface area compared to the second surface area is to expose the substrate to the organic matter And the steps in the solution of the solvent. The method according to claim 7, wherein the solution contains the organic substance represented by the above general formula (1) in an amount of 0.1% by mass or more and 10% by mass or less with respect to the total of the organic substance and the solvent. The method according to claim 7 or 8, wherein after selectively depositing a film of the organic substance represented by the general formula (1) on the substrate, the substrate is washed with a solvent. The method according to any one of claims 1 to 6, wherein the step of selectively depositing a film of an organic substance represented by the general formula (1) on the first surface area is more preferred than the second surface area It is a step of exposing the substrate to an atmosphere containing a gas of the organic substance. The method according to claim 10, wherein the temperature range of the atmosphere is 0°C or more and 200°C or less. The method of claim 10 or 11, wherein the pressure range of the above atmosphere is 13 Pa or more and 67 kPa or less. The method according to any one of claims 1 to 12, wherein the ratio of the thickness t ₁ of the organic film on the first surface area to the thickness t ₂ of the organic film on the second surface area (t ₁ /t ₂ ) 5 or more. A substrate characterized in that it has a structure in which both a first surface area containing metal and a second surface area containing non-metallic inorganic material and/or metal oxide are exposed, and has a lower surface in the first surface area The film of the organic substance represented by the general formula (1) does not have the film of the organic substance in the second surface area, or the thickness t ₂ of the film of the organic substance on the second surface area is thinner than the first surface area The thickness t ₁ of the film of the above organic matter; [Chem 2]

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ , and R ⁴ are The hydrogen atom may be a hydrocarbon group having a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; wherein the hydrocarbon may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more). A deposited film of organic matter, characterized in that it is a film of organic matter formed by the method as claimed in any one of claims 1 to 13, and is selectively deposited on a substrate, the organic matter is represented by the following general formula (1) ; [化3]

(In general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ , and R ⁴ are The hydrogen atom may be a hydrocarbon group having a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; wherein the hydrocarbon may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more). An organic substance characterized by the method used in any one of claims 1 to 13 and represented by the following general formula (1);

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ , and R ⁴ are The hydrogen atom may be a hydrocarbon group having a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; wherein the hydrocarbon may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more). A solution characterized by containing an organic substance and a solvent characterized by the following general formula (1); [化5]

(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R ¹ is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R ² , R ³ , and R ⁴ are The hydrogen atom may be a hydrocarbon group having a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; wherein the hydrocarbon may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more). The solution according to claim 17, wherein the organic substance is selected from the group consisting of o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2-(ethylamino)ethanol, 2-aminoethylthiol , At least one of the group consisting of 3-amino-1-propanol and o-aminophenol, The above solvent is at least one selected from the group consisting of ethanol and isopropanol, The said solution contains the organic substance represented by the said general formula (1) with respect to the total of organic substance and solvent 0.1 mass% or more and 10 mass% or less.